Mesostructured Zeolitic Materials and Methods of Making and Using the Same

ABSTRACT

One aspect of the present invention relates to mesostructured zeolites. The invention also relates to a method of preparing mesostructured zeolites, as well as using them as cracking catalysts for organic compounds and degradation catalysts for polymers.

GOVERNMENT FUNDING

This invention was made with support under Grant Number DAAD19-02-D0002,awarded by the Army Research Office; the government, therefore, hascertain rights in the invention.

BACKGROUND OF THE INVENTION

Zeolites and related crystalline molecular sieves are widely used due totheir regular microporous structure, strong acidity, and ion-exchangecapability. van Bekkum, H., Flanigen, E. M., Jacobs, P. A., Jansen, J.C. (editors), Introduction to Zeolite Science and Practice, 2nd edition.Studies in Surface Science and Catalysis, Vol. 137 (2001); Corma, A.,Chem. Rev., 1997, 97, 2373-2419; Davis, M. E., Nature, 2002, 417,813-821. However, their applications are limited by their small poreopenings, which are typically narrower than 1 nm. The discovery ofMCM-41, with tuneable mesopores of 2-10 nm, overcomes some of thelimitations associated with zeolites. Corma, A., Chem. Rev., 1997, 97,2373-2419; Kresge, C. T., et al., Nature, 1992, 259, 710-712; Kosslick,H., et al., Appl Catal. A: Gen., 1999, 184, 49-60; Linssen, T.,Cassiers, K., Cool, P., Vansant, E. F., Adv. Coll. Interf. Sci., 2003,103, 121-147. However, unlike zeolites, MCM-41-type materials are notcrystalline, and do not possess strong acidity, high hydrothermalstability and high ion-exchange capability, which are important forcertain catalytic applications. Corma, A., Chem. Rev., 1997, 97,2373-2419.

Over the past 10 years, a great deal of effort has been devoted tounderstanding and improving the structural characteristics of MCM-41. Itwas found that the properties of Al-MCM-41 could be improved through (i)surface silylation, (ii) Al grafting on the pore walls to increaseacidity, (iii) salt addition during synthesis to facilitate thecondensation of aluminosilicate groups, (iv) use of organics typicallyemployed in zeolite synthesis to transform partially the MCM-41 wall tozeolite-like structures, (v) preparation of zeolite/MCM-41 composites,(vi) substitution of cationic surfactants by tri-block copolymers andGemini amine surfactants to thicken the walls, and (vii) assembly ofzeolite nanocrystals into an ordered mesoporous structure. Liu, Y.,Pinnavaia, T. J., J. Mater. Chem., 2002, 12, 3179-3190. In the latterapproach, Liu et al. were able to prepare the first steam-stablehexagonal aluminosilicate (named MSU-S) using zeolite Y nanoclusters asbuilding blocks. Pentasil zeolite nanoclusters were also used to produceMSU-S_((MFI)) and MSU-S_((BEA))).

Some strategies have managed to improve appreciably the acidicproperties of Al-MCM-41 materials. Liu, Y., Pinnavaia, T. J., J. Mater.Chem., 2002, 12, 3179-3190; van Donk, S., et al., Catal. Rev., 2003, 45,297-319; Kloetstra, K. R., et al., Chem. Commun., 1997, 23, 2281-2282;Corma, A., Nature, 1998, 396, 353-356; Karlsson, A., et al., MicroporousMesoporous Mater., 1999, 27, 181-192; Jacobsen, C. J. H., et al., J. Am.Chem. Soc., 2000, 122, 7116-7117; Huang L., et al., J. Phys. Chem. B.,2000, 104, 2817-2823; On, D. T., et al., Angew. Chem. Int. Ed., 2001,17, 3248-3251; Liu, Y., et al., Angew. Chem. Int. Ed., 2001, 7,1255-1258. However, due to the lack of long-range crystallinity in thesematerials, their acidity was not as strong as those exhibited byzeolites. Corma, A., Chem. Rev., 1997, 97, 2373-2419. For example,semicrystalline mesoporous materials, such as nanocrystallinealuminosilicate PNAs and Al-MSU-S_((MFI)), even being more active thanconventional Al-MCM-41, showed significantly lower activity than H-ZSM-5for cumene cracking; the catalyst activity for this reaction has usuallybeen correlated to the Bronsted acid strength of the catalyst. Corma,A., Chem. Rev., 1997, 97, 2373-2419; Liu, Y., Pinnavaia, T. J., J.Mater. Chem., 2002, 12, 3179-3190; Kloetstra, K R., et al., Chem.Commun., 1997, 23, 2281-2282; Jacobsen, C. J. H., et al., J. Am. Chem.Soc., 2000, 122, 7116-7117.

Previous attempts to prepare mesostructured zeolitic materials have beenineffective, resulting in separate zeolitic and amorphous mesoporousphases. Karlsson, A., et al., Microporous Mesoporous Mater., 1999, 27,181-192; Huang L., et al., J. Phys. Chem. B., 2000, 104, 2817-2823.Moreover, some authors pointed out the difficulty of synthesizingthin-walled mesoporous materials, such as MCM-41, with zeoliticstructure, due to the surface tension associated with the high curvatureof the mesostructure. Liu, Y., Pinnavaia, T. J., J. Mater. Chem., 2002,12, 3179-3190. Thus, the need exists for zeolite single crystals withordered mesoporosity, and methods of making and using them.

SUMMARY OF THE INVENTION

In one aspect, the present invention relates to a crystalline inorganicmaterial organized in a mesostructure. In a further embodiment, theinorganic material is a metal oxide. In a further embodiment, theinorganic material is a zeolite. In a further embodiment, the inorganicmaterial is a zeotype. In a further embodiment, the inorganic materialhas a faujasite, mordenite, or ZSM-5 (MFI) structure. In a furtherembodiment, the mesostructure has the hexagonal pore arrangement ofMCM-41. In a further embodiment, the mesostructure has the cubic porearrangement of MCM-48. In a further embodiment, the mesostructure hasthe lamellar pore arrangement of MCM-50. In a further embodiment, themesostructure has pores organized in a foam arrangement. In a furtherembodiment, the mesostructure has randomly placed pores.

In a further embodiment, the mesostructure is a one dimensionalnanostructure. In a further embodiment, the nanostructure is a nanotube,nanorod, or nanowire.

In a further embodiment, the mesostructure is a two dimensionalnanostructure. In a further embodiment, the nanostructure is a nanoslab,nanolayer, or nanodisc.

In a further embodiment, the crystalline inorganic material isY[MCM-41], MOR[MCM-41], or ZSM-S[MCM41].

In a further embodiment, the mean pore diameter within the mesostructureis about 2 to about 5 nm. In a further embodiment, the mean porediameter within the mesostructure is about 2 to about 3 nm. In a furtherembodiment, the wall thickness within the mesostructure is about 1 toabout 5 nm. In a further embodiment, the wall thickness within themesostructure is about 1 to about 3 nm.

In another aspect, the present invention relates to a method ofpreparing a mesostructured zeolite comprising: a) adding a zeolite to amedium comprising an acid or base, and optionally a surfactant; b)adding a surfactant to the medium from step a) if it is not therealready; c) optionally adding a swelling agent to the medium from stepb); d) optionally hydrothermally treating the medium from step b) or c);and e) washing and drying the resulting material.

In a further embodiment, the resulting material is further calcined atelevated temperatures. In a further embodiment, the calcination step isperformed in air or oxygen. In a further embodiment, the calcinationstep is performed in an inert gas. In a further embodiment, the inertgas is N₂. In a further embodiment, the maximum elevated temperaturesare at about 500 to 600° C. In a further embodiment, the maximumelevated temperatures are at about 550° C.

In a further embodiment, the zeolite is selected from the groupconsisting of faujasite (FAU), mordenite (MOR), and ZSM-5 (MFI). In afurther embodiment, the medium in step a) comprises a base. In a furtherembodiment, the base is an alkali hydroxide, alkaline earth hydroxide,NH₄OH or a tetralkylammonium hydroxide. In a further embodiment, thebase is NaOH, NH₄OH, or tetramethylammonium hydroxide. In a furtherembodiment, the medium in step a) comprises an acid. In a furtherembodiment, the acid is HF. In a further embodiment, the surfactant isan alkylammonium halide. In a further embodiment, the surfactant is acetyltrimethylammonium bromide (CTAB) surfactant. In a furtherembodiment, hydrothermally treating the medium from step b) or c) occursat about 100 to about 200° C. In a further embodiment, hydrothermallytreating the medium from step b) or c) occurs at about 120 to about 180°C. In a further embodiment, hydrothermally treating the medium from stepb) or c) occurs at about 140 to about 160° C. In a further embodiment,hydrothermally treating the medium from step b) or c) occurs at about150° C. In a further embodiment, hydrothermally treating the medium fromstep b) or c) takes place overnight. In a further embodiment,hydrothermally treating the medium from step b) or c) takes place overabout 20 hours.

In another aspect, the present invention relates to a mesostructuredzeolite prepared by any of the aforementioned methods.

In another aspect, the present invention relates to a method ofpreparing a mesostructured zeolite comprising: a) adding a zeolite inits acidic form to a medium comprising a base, and optionally asurfactant, in which the zeolite is partially dissolved to produce asuspension; b) adding a surfactant to the medium from step a) if it isnot there already; c) optionally adding a swelling agent to the mediumfrom step b); d) optionally hydrothermally treating the medium from stepb) or c); e) washing and drying the resulting material; and f) removingthe surfactant from the resulting material either by calcining atelevated temperatures, or by solvent extraction.

In another aspect, the present invention relates to a mesostructuredzeolite prepared by the above method, wherein the mesostructured zeoliteis in the form of a nanotube, nanorod, or nanowire.

In another aspect, the present invention relates to a mesostructuredzeolite prepared by the above method, wherein the mesostructured zeoliteis in the form of a nanoslab, nanolayer, or nanodisc.

In another aspect, the present invention relates to a method ofanchoring a positively charged chemical species to a mesostructuredzeolite comprising contacting the mesostructured zeolite and thepositively charged species in a medium. In a further embodiment, thepositively charged species is selected from the group consisting ofcations of an element, quaternary amines, ammonium ions, pyridiniumions, phosphonium ions, and mixtures thereof.

In another aspect, the present invention relates to a method ofanchoring a chemical species to a mesostructured zeolite comprising:contacting the mesostructured zeolite in its acidic form and a basicchemical species in a medium. In a further embodiment, the basicchemical species is an inorganic base or an organic base. In a furtherembodiment, the basic chemical species is selected from the groupconsisting of hydroxide, amine, pyridine, phosphine, and mixturesthereof.

In another aspect, the present invention relates to a method ofanchoring a homogeneous catalyst on a mesostructured zeolite comprising:contacting a mesostructured zeolite comprising a chemical speciesanchored on it, and a homogeneous catalyst in a medium, wherein theanchored chemical species is capable of acting as a ligand to thehomogeneous catalyst.

In another aspect, the present invention relates to a method ofsupporting a heterogeneous catalyst on a mesostructured zeolitecomprising contacting the mesostructured zeolite and the heterogeneouscatalyst by a method selected from the group consisting of physicalmixture, dry impregnation, wet impregnation, incipient wet impregnation,ion-exchange, and vaporization. In a further embodiment, theheterogeneous catalyst comprises a metal or a mixture thereof. In afurther embodiment, the heterogeneous catalyst comprises a metal oxideor a mixture thereof. In a further embodiment, the heterogeneouscatalyst comprises a nanoparticle, cluster, or colloid.

In another aspect, the present invention relates to a method ofcatalytically cracking an organic compound comprising contacting theorganic compound with a mesostructured zeolite. In a further embodiment,the organic compound is a hydrocarbon. In a further embodiment, theorganic compound is an unsaturated hydrocarbon. In a further embodiment,the organic compound is an aromatic hydrocarbon. In a furtherembodiment, the organic compound is an alkylated benzene. In a furtherembodiment, the organic compound is 1,3,5-triisopropyl benzene. In afurther embodiment, the organic compound is crude oil. In a furtherembodiment, the organic compound is gas-oil. In a further embodiment,the organic compound is vacuum gas oil. In a further embodiment, themesostructured zeolite has the zeolitic structure of a faujasite (FAU),mordenite (MOR), or ZSM-5 (MFI). In a further embodiment, themesostructured zeolite has the hexagonal pore arrangement of MCM-41. Ina further embodiment, the mesostructured zeolite is Y[MCM-41],MOR[MCM-41], or ZSM-5[MCM-41].

In another aspect, the present invention relates to a method of refiningcrude oil comprising contacting the crude oil with a mesostructuredzeolite. In a further embodiment, the contacting of the oil with themesostructured zeolite takes place within a Fluid Catalytic CrackingUnit. In a further embodiment, production of gasoline is increasedrelative to the amount of gasoline produced in the absence of themesostructured zeolite. In a further embodiment, production of lightolefins is increased relative to the amount of light olefins produced inthe absence of the mesostructured zeolite.

In another aspect, the present invention relates to a method ofcatalytically degrading a polymer comprising contacting the polymer witha mesostructured zeolite. In a further embodiment, the polymer is ahydrocarbon polymer. In a further embodiment, the polymer is apoly(alkylene), poly(alkynyl) or poly(styrene). In a further embodiment,the polymer is polyethylene (PE). In a further embodiment, themesostructured zeolite has the zeolitic structure of a faujasite (FAU),mordenite (MOR), or ZSM-5 (MFI). In a further embodiment, themesostructured zeolite has the hexagonal pore arrangement of MCM-41. Ina further embodiment, the mesopostructured zeolite is Y[MCM-41],MOR[MCM-41], or ZSM-5[MCM-41].

These embodiments of the present invention, other embodiments, and theirfeatures and characteristics, will be apparent from the description,drawings and claims that follow.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts the X-ray diffraction pattern of the mesostructuredzeolite H—Y[MCM-41]. Both the ordered mesostructure (reveled by the XRDpeaks at low angles) and the zeolitic crystalline structure are present.

FIG. 2 depicts the X-ray diffraction pattern of the mesostructuredzeolite H-MOR[MCM-41]. Both the ordered mesostructure (reveled by theXRD peaks at low angles) and the zeolitic crystalline structure arepresent.

FIG. 3 depicts the X-ray diffraction pattern of the mesostructuredzeolite H-ZSM-5[MCM-41]. Both the ordered mesostructure (reveled by theXRD peaks at low angles) and the zeolitic crystalline structure arepresent.

FIG. 4 depicts FTIR characterization peaks for MCM-41, zeolite Y, andMeso H—Y.

FIG. 5 depicts FTIR spectra of H—Y[MCM-41] (top), H-MOR[MCM-41](middle), H-ZSM-5[MCM-41] (bottom) and their zeolitic versions. A matchbetween each mesostructured zeolite and its corresponding zeolite isobserved, indicating the fully zeolitic connectivity present inmesostructured zeolites.

FIG. 6 depicts the physisorption isotherm of N₂ at 77 K of H—Y[MCM-41]and its zeolitic version. The pore size distribution (BJH method) of themesostructured zeolite is included in inset. The presence of welldeveloped narrow pore size mesoporosity in the mesolitic sample isevident.

FIG. 7 depicts the physisorption isotherm of N₂ at 77 K of H-MOR[MCM-41]and its zeolitic version. The pore size distribution (BJH method) of themesostructured zeolite is included in inset. The presence of welldeveloped narrow pore size mesoporosity in the mesolitic sample isevident.

FIG. 8 depicts the physisorption isotherm of N₂ at 77 K ofH-ZSM-5[MCM-41] and its zeolitic version. The pore size distribution(BJH method) of the mesostructured zeolite is included in inset. Thepresence of well developed narrow pore size mesoporosity in themesolitic sample is evident.

FIG. 9 depicts pore volumes (darker columns) of H—Y[MCM-41],H-MOR[MCM-41], and H-ZSM-5[MCM-41] and their zeolitic versions (lightercolumns).

FIG. 10 depicts images obtained by transmission electron microscopic ofa) detail of a H—Y[MCM-41] mesostructured zeolite, and b) detail of aH—Y[MCM-41] mesostructured zeolite at different focus. The electrondiffraction patterns are included as insets.

FIG. 11 depict a TEM image of a mesostructured zeolite of the presentinvention.

FIG. 12 depicts a TEM image of a mesostructured zeolite of the presentinvention.

FIG. 13 depicts catalytic cracking of 1,3,5-triisopropyl benzene tobenzene by zeolite HY.

FIG. 14 depicts the process of catalytic cracking of 1,3,5-triisopropylbenzene to 1,3-diisopropyl benzene by a mesostructured zeolite of thepresent invention. Diisopropyl benzene was the only product detected.

FIG. 15 depicts catalytic activity for 1,3,5-triisopropyl benzenecracking shown as conversion vs. time for H—Y[MCM-41], its zeoliticversion, and a conventional Al-MCM-41. A 50 mL/min of He flow saturatedwith 1,3,5-triisopropylbenzene at 120° C. was flowed at 200° C. over 50mg of catalyst.

FIG. 16 depicts the catalytic cracking of 1,3,5-triisopropyl benzenewith H—Y[MCM-41] to diisopropyl benzene and cumene. Compared to acommercial sample, catalytic cracking with H—Y[MCM-41] results in higherselectivity and reduction in benzene production.

FIG. 17 depicts the hydrothermal stability of H—Y[MCM-41] compared tothe non-mesolytic zeolite Al-MCM-41.

FIG. 18 depicts catalytic activity for 1,3,5-triisopropyl benzenecracking shown as conversion vs. time for H-MOR[MCM-48], and itszeolitic version. A 50 mL/min of He flow saturated with1,3,5-triisopropylbenzene at 120° C. was flowed at 200° C. over 50 mg ofcatalyst.

FIG. 19 depicts catalytic activity for 1,3,5-triisopropyl benzenecracking shown as conversion vs. time for H-ZSM-5[MCM-41], and itszeolitic version. A 50 mL/min of He flow saturated with1,3,5-triisopropylbenzene at 120° C. was flowed at 200° C. over 50 mg ofcatalyst.

FIG. 20 depicts the conversion of 1,3,5-triisopropylbenzene versus timefor H-MOR[ZNR] and H-MOR. The ratio benzene produced by H-MOR/benzeneproduced by H-MOR[ZNR] as a function of time is also shown. A heliumflow of 50 mL/min saturated with 1,3,5-triisopropylbenzene at 120° C.was introduced over 50 mg of catalyst at 200° C.

FIG. 21 depicts percentage of polyethylene (PE) weight lost vs.temperature for the mixtures PE:catalysts: 2:1 wt., 1:1 wt., and 1:2wt., for H-ZSM-5[MCM-41] and H-ZSM-5.

FIG. 22 depicts the FTIR spectra of a) H—Y[MCM-41], b) NH₄—Y[MCM41], c)NH₂(CH₂)₂NMe₃Cl, d) NH₂(CH₂)₂NMe₃—Y[MCM-41], d) Rh(PPh₃)₃Cl, and e)Rh(PPh₃)₃NH₂(CH₂)₂NMe₃—Y[MCM-41].

DETAILED DESCRIPTION OF THE INVENTION Definitions

For convenience, before further description of the present invention,certain terms employed in the specification, examples, and appendedclaims are collected here. These definitions should be read in light ofthe remainder of the disclosure and understood as by a person of skillin the art.

The articles “a” and “an” are used herein to refer to one or more thanone (i.e., at least one) of the grammatical object of the article. Byway of example, “an element” means one element or more than one element.

The term “catalyst” is art-recognized and refers to any substance thatnotably affects the rate of a chemical reaction without itself beingconsumed or significantly altered.

The terms “comprise” and “comprising” are used in the inclusive, opensense, meaning that additional elements may be included.

The term “cracking” is art-recognized and refers to any process ofbreaking up organic compounds into smaller molecules.

The term “including” is used to mean “including but not limited to”.“Including” and “including but not limited to” are used interchangeably.

“MCM41” represents a Mobil composite of matter and refers to anamorphous mesoporous silica with a hexagonal pore arrangement, whereinthe mean pore diameter is in the range of about 2-10 nm.

“MCM-48” represents a Mobil composite of matter and refers to anamorphous mesoporous silica with a cubic pore arrangement, wherein themean pore diameter is in the range of about 2-10 nm.

“MCM-50” represents a Mobil composite of matter and refers to anamorphous mesoporous silica with a lamellar pore arrangement, whereinthe mean pore diameter is in the range of about 2-10 nm.

The term “mesoporous” is art-recognized and refers to a porous materialcomprising pores with an intermediate size, ranging anywhere from about2 to about 50 nanometers.

The term “mesostructure” is art-recognized and refers to a structurecomprising mesopores which control the architecture of the material atthe mesoscopic or nanometer scale, including ordered and non-orderedmesostructured materials, as well as nanostructured materials, i.e.materials in which at least one of their dimension is in the nanometersize range, such as nanotubes, nanorings, nanorods, nanowires,nanoslabs, and the like.

The term “mesostructured zeolites” as used herein includes allcrystalline mesoporous materials, such as zeolites, aluminophosphates,gallophosphates, zincophosphates, titanophosphates, etc. Itsmesostructure maybe in the form of ordered mesporosity (as in, forexample MCM-41, MCM-48 or SBA-15), non-ordered mesoporosity (as inmesocellular foams (MCF)), or mesoscale morphology (as in nanorods andnanotubes). The notation zeolite[mesostructure] is used to designate thedifferent types of mesostructured zeolites.

“MOR” represents a mordenite which is a zeolite comprising approximately2 moles of sodium and potassium and approximately 1 mole of calcium inits orthorhombic crystal structure. This term also includes the acidicform of MOR which may also be represented as “H-MOR.”

“MSU-S (MFI)” represents a mesoporous material made with nanosizedzeolites with a pore range of about 2-15 nm. The (MFI) refers to itsstructure.

“MSU-S (BEA)” represents a mesoporous material made with nanosizedzeolites with a pore range of about 1-15 nm. The (BEA) refers to itsstructure.

“PNA” represents a semicrystallized form of MCM-41.

“SBA-15” represents mesoporous (alumino) silicas with pore diameters upto 30 nm arranged in a hexagonal manner and pore walls up to 6 nm thick.

The term “surfactant” is art-recognized and refers to any surface-activeagent or substance that modifies the nature of surfaces, often reducingthe surface tension of water. Cetyltrimethylammonium bromide is anon-limiting example of a surfactant.

“Y” represents a faujasite which is a zeolite comprising 2 moles ofsodium and 1 mole of calcium in its octahedral crystal structure. Thisterm also includes the acidic form of Y which may also be represented as“H—Y.”

The term “zeolite” is defined as in the International ZeoliteAssociation Constitution (Section 1.3) to include both natural andsynthetic zeolites as well as molecular sieves and other microporous andmesoporous materials having related properties and/or structures. Theterm “zeolite” also refers to a group, or any member of a group, ofstructured aluminosilicate minerals comprising cations such as sodiumand calcium or, less commonly, barium, beryllium, lithium, potassium,magnesium and strontium; characterized by the ratio(Al+Si):O=approximately 1:2, an open tetrahedral framework structurecapable of ion exchange, and loosely held water molecules that allowreversible dehydration. The term “zeolite” also includes“zeolite-related materials” or “zeotypes” which are prepared byreplacing Si⁴⁺ or Al³⁺ with other elements as in the case ofaluminophosphates (e.g., MeAPO, SAPO, ElAPO, MeAPSO, and ElAPSO),gallophosphates, zincophophates, titanosilicates, etc.

“ZSM-5” or “ZSM-5 (MFI)” represents a Mobil synthetic zeolite-5. Thisterm also includes the acidic form of ZSM-5 which may also berepresented as “H-ZSM-5.” The (MFI) relates to its structure.

A comprehensive list of the abbreviations utilized by organic chemistsof ordinary skill in the art appears in the first issue of each volumeof the Journal of Organic Chemistry; this list is typically presented ina table entitled Standard List of Abbreviations.

For purposes of this invention, the chemical elements are identified inaccordance with the Periodic Table of the Elements, CAS version,Handbook of Chemistry and Physics, 67th Ed., 1986-87, inside cover.

Contemplated equivalents of the zeolitic structures, subunits and othercompositions described above include such materials which otherwisecorrespond thereto, and which have the same general properties thereof(e.g., biocompatible), wherein one or more simple variations ofsubstituents are made which do not adversely affect the efficacy of suchmolecule to achieve its intended purpose. In general, the compounds ofthe present invention may be prepared by the methods illustrated in thegeneral reaction schemes as, for example, described below, or bymodifications thereof, using readily available starting materials,reagents and conventional synthesis procedures. In these reactions, itis also possible to make use of variants which are in themselves known,but are not mentioned here.

Synthesis of Mesostructured Zeolites

In recent years, expertise has been gained in the synthesis of zeoliteswith desired properties by the choice of the organic molecule used asstructure directing agent (SDA), control of the synthesis conditions,and post-synthesis treatments. van Bekkum, H., Flanigen, E. M., Jacobs,P. A., Jansen, J. C. (editors) Introduction to Zeolite Science andPractice, 2nd edition. Studies in Surface Science and Catalysis, 2001,137; Corma, A., Chem. Rev., 1997, 97, 2373-2419; Davis, M. E., Nature,2002, 417, 813-821; Davis, M. E., et al., Chem. Mater., 1992, 4,756-768; de Moor P-P. E. A. et al., Chem. Eur. J., 1999, 5(7),2083-2088; Galo, J. de A. A., et al., Chem. Rev., 2002, 102, 4093-4138.At the same time, the family of ordered mesoporous materials has beengreatly expanded by the use of different surfactants and synthesisconditions. Corma, A., Chem. Rev., 1997, 97, 2373-2419; Davis, M. E.,Nature, 2002, 417, 813-821; Galo, J. de A. A., et al., Chem. Rev., 2002,102, 4093-4138; Ying, J. Y., et al., Angew. Chem. Int. Ed., 1999, 38,56-77. The family of mesostructured zeolites disclosed herein is aone-phase hybrid material consisting of a zeolitic structure withcontrolled mesoporosity, which bridges the gap between crystallinemicroporous and amorphous mesoporous materials.

The synthesis of mesostructured zeolites is applicable to a wide varietyof materials. The first strategy is based on the short-rangereorganization of a zeolite structure in the presence of a surfactant toaccommodate mesoporosity without loss of zeolitic crystallinity. In anexemplary synthesis, a zeolite is added to a diluted NH₄OH solutioncontaining cetyltrimethylammonium bromide (CTAB) surfactants. Themixture is hydrothermally treated at about 100 to about 200° C., about120 to about 180° C., about 140 to about 160° C., or about 150° C. forabout 20 hr or overnight during which the zeolite structure undergoesshort-range rearrangements to accommodate the MCM-41 type ofmesostructure. Higher surfactant concentrations and longer hydrothermaltreatments would produce mesostructured zeolites with the MCM-48 type ofmesostructure. After washing and drying, the resulting material iscalcined in N₂ at a maximum temperature from about 500 to 600° C., or atabout 550° C.; and then in air for surfactant removal. This syntheticscheme could be used to produce mesostructured zeolites with variouszeolitic structures. For zeolites with a low solubility (e.g. ZSM-5), adiluted tetramethyl ammonium hydroxide (TMA—OH) or a solution of HFwould be used instead of a diluted NH₄OH solution in the synthesisscheme.

The mesopore size and architecture may also be conveniently tuned bywell-known techniques, such as the use of surfactants with differentaliphatic chain lengths, non-ionic surfactants, triblock copolymers,swelling agents, etc. Also, post-synthesis treatments (e.g., silanation,grafting, surface functionalization, ion-exchange, immobilization ofhomogeneous catalysts and deposition of metal nanoclusters) could beemployed to further improve the textural properties of the materialsand/or modify their surface chemistry.

A second approach is based on the dissolution of a zeolite either in anacidic or basic medium, followed by hydrothermal treatment in thepresence of a surfactant. Under these conditions, a mesoporous solid wasobtained wherein the pore walls were amorphous initially. The pore wallsare later transformed to a zeolitic phase, with or without affecting themesoporous structure. Zeolitic nanorods (ZNRs) have been prepared bythis approach in three steps: (i) basic treatment of a zeolite toproduce a suspension of amorphous aluminosilicate, (ii) surfactantaddition to produce MCM-41, and (iii) hydrothermal treatment of theresulting solid. During the last step, the MCM-41 mesostructuretransformed first to MCM-48 and then to MCM-50, while their amorphouspore walls transformed to a crystalline zeolitic phase.

Zeolite-like materials, which represent a growing family of inorganicand organic/inorganic molecular sieves, may also be used as precursorsfor the synthesis of mesostructured zeolites, since the syntheticapproaches described above may be adapted for a wide variety ofmaterials.

Structure of Mesostructured Zeolites

The hybrid structure of the mesostructured zeolites was studied via XRD.FIGS. 1-3 show the XRD patterns of H—Y[MCM-41], H-MOR[MCM-41], andH-ZSM-5[MCM41], respectively. Very intense peaks, both at low and high2θ° values reveal both the ordered mesostructure and the zeoliticcrystallinity of this family of materials. In all cases, the peaks atlow 2θ° values can be indexed to hexagonal symmetry indicating thepresence of MCM-41, whereas the well-defined XRD peaks at high 2θ°values correspond, respectively, to the zeolites Y, MOR and ZSM-5. Thisobservation is remarkable since no long-range crystallinity has beenpreviously observed in mesoporous metal oxides and onlysemicrystallinity (due to the presence of zeolite nanoclusters) has beenachieved in thick-wall mesoporous materials prepared using triblockcopolymers. Kloetstra, K. R., et al., Chem. Commun, 1997, 23, 2281-2282;Liu, Y. et al., Angew. Chem. Int. Ed. 2001, 7, 1255-1258; On, D. T., etal., Angew. Chem. Int. Ed., 2001, 17, 3248-3251.

The connectivity of the mesostructured zeolites was studied by infraredspectroscopy (FTIR) (See FIGS. 4-5). FIG. 5 shows a remarkable matchbetween the IR spectra of H—Y[MCM-41], H-MOR[MCM-41], andH-ZSM-5[MCM-41] and those of the their corresponding zeolitic versions,contrary to highly stable Al-MCM-41, which presents only one IR broadpeak, due to imperfect zeolitic connectivity. Liu, Y., Pinnavaia, T. J.,J. Mater. Chem., 2002, 12, 3179-3190; Kloetstra, K. R., et al., Chem.Commun, 1997, 23, 2281-2282; Liu, Y. et al., Angew. Chem. Int. Ed.,2001, 7, 1255-1258. The peak at 960 cm⁻¹ in the H—Y[MCM-41]mesostructured zeolite sample, characteristic of silanol groups on thewall surfaces, is an additional evidence of the mesoporous/zeolitichybrid nature of mesostructured zeolites. Geidel, E., et al.,Microporous and Mesoporous Materials, 2003, 65, 31-42.

The presence of well-defined mesoporosity in mesostructured zeolites canbe suitably studied by nitrogen physisorption at 77 K. Storck, S., etal., Applied Catalysis A: General, 1998, 17, 137-146. FIGS. 6-8 show thenitrogen isotherms at 77 K of H—Y[MCM-41], H-MOR[MCM-41], andH-ZSM-5[MCM-41], respectively, and their zeolitic versions. Conventionalzeolites adsorb nitrogen only at low pressures, producing type Iisotherms that are characteristic of microporous materials. Storck, S.,et al., Applied Catalysis A: General, 1998, 17, 137-146. However, themesostructured zeolites show sharp nitrogen uptakes at higher partialpressures (P/P₀˜0.3), which is a characteristic feature ofmesostructured materials with narrow pore-size distribution (porediameter ˜2.5 nm). Storck, S., et al., Applied Catalysis A: General,1998, 17, 137-146. Compared to zeolites, mesostructured zeolites havemore than double the pore volume (see FIG. 9) due to the incorporationof well-developed, narrow-sized mesoporosity, mesostructured zeoliteshave sharper uptake at low partial pressures, which indicates thepresence of microporosity, and slightly higher pore size. As well knownin surfactant-templated mesoporous solids synthesis, the size of themesopore in mesostructured zeolites can be easily tuned by changing thelength of the aliphatic chain of the surfactant. Corma, A., Chem. Rev.1997, 97, 2373-2419; Linssen, T., Cassiers, K., Cool, P., Vansant, E.F., Advances in Colloid and Interface Science, 2003, 103, 121-147; Ying,J. Y., et al., Angew. Chem. Int. Ed., 1999, 38, 56-77.

Previous attempts by others to prepare zeolitic mesostructured materialsled to phase separation into zeolite and amorphous mesoporous solids.Karlsson, A., et al., Microporous and Mesoporous Materials, 1999, 27,181-192; Huang L., et al., J. Phys. Chem. B. 2000, 104, 2817-2823.Moreover, some authors pointed out the difficulty of making thin-walledmesoporous materials, such as MCM-41, with zeolitic walls, due tosurface tension caused by the high curvature of the structure. Yang, P.,et al., Nature, 1998, 396, 152-155.

Direct evidence for the hybrid single-phase nature of mesostructuredzeolites was obtained via transmission electronic microscopy (TEM).FIGS. 10 a and 10 b show two details of the mesostructured zeolitemicrostructure at different foci in which both the crystallinity andordered mesoporosity can be observed in a single phase. Additional TEMimages are depicted in FIGS. 11-12.

Additional evidence of the hybrid nature of mesostructured zeolitescomes from catalysis. The presence of mesopores, high surface, and verythin walls (˜2 nm), must allow access to bulkier molecules and reduceintracrystalline diffusion. So, enhanced catalytic activity for bulkymolecules must be observed in mesostructured zeolites compared tozeolites.

For example, semicrystalline mesoporous materials, such asnanocrystalline aluminosilicates PNAs and Al-MSU-S_((MFI)), showssignificantly lower activity for cumene cracking (which is usuallycorrelated to strong Bronsted acidity) than conventional H-ZSM-5.Mesostructured zeolites, however, show even greater activity thanzeolites, most likely due to their fully zeolitic structure and thepresence of mesopores. For example, H-ZSM-5[MCM41] converts 98% ofcumene at 300° C. whereas commercial H-ZSM-5 converts 95% in similarconditions.

The anchoring of chemical species on mesostructured zeolites wasconfirmed by Infrared Spectroscopy (FTIR). The pure chemical species tobe anchored, the mesostructured zeolites, and the species modifiedmesostructured zeolites prepared according the method described hereinwere all analyzed by FTIR. The species modified mesostructured zeolitesexhibited the FTIR bands of the chemical species which did not disappearafter washing the samples.

Some of the chemical species anchored on mesostructured zeolites wereused as ligands for a homogeneous catalysts. This anchoring of ahomogeneous catalyst was confirmed by Infrared Spectroscopy (FTIR), andby catalytic testing of both the homogeneous catalysts and thehomogeneous catalysts anchored on the mesostructured zeolite. Theseexperiments were repeated after washing the samples and no major changeswere observed, indicating that this method is suitable for anchoringboth chemical species and homogeneous catalysts.

Applications

The unique structure of mesostructured zeolites will be useful to avariety of fields, and should address certain limitations associatedwith conventional zeolites. As catalysis is the most important field ofapplication for zeolites, special emphasis is placed on the catalyticapplications of mesostructured zeolites. van Bekkum, H., Flanigen, E.M., Jacobs, P. A., Jansen, J. C. (editors). Introduction to ZeoliteScience and Practice, 2nd edition. Studies in Surface Science andCatalysis, 2001, Vol. 137; Corma, A., Chem. Rev. 1997, 97, 2373-2419;Davis, M. E., Nature 2002, 417, 813-821.

The combination of a mesostructure, a high surface-area, and thin walls(˜2 nm) should provide for access to bulky molecules and reduce theintracrystalline diffusion barriers. Thus, enhanced catalytic activityfor bulky molecules should be observed over mesostructured zeolites, ascompared to conventional zeolites. See FIGS. 13-14.

Acid catalysts with well-defined ultralarge pores are highly desirablefor many applications, especially for catalytic cracking of the gas oilfraction of petroleum, whereby slight improvements in catalytic activityor selectivity would translate to significant economic benefits. Venuto,P. B., Habib, E. T., Jr. Fluid Catalytic Cracking with ZeoliteCatalysts. Marcel Dekker, New York, 1979; Harding, R. H., et al., Appl.Catal. A: Gen., 2001, 221, 389-396; Degnan, T. F., et al., MicroporousMesoporous Mater., 2000, 35-36, 245-252. As a test reaction, we haveexamined the catalytic cracking of 1,3,5-triisopropylbenzene (criticaldimension ˜0.95 nm). The H—Y[MCM41] mesostructured zeolite demonstratedsuperior catalytic activity for this cracking reaction after 400 min at200° C. (93% conversion) compared to the H—Y zeolite (71% conversion)and the mesoporous Al-MCM-41 (39% conversion) (see FIG. 15). This resultwas attributed to its combination of strong acidity and mesostructurednature. The mesopores greatly facilitated the hydrocarbon diffusionwithin the H—Y[MCM-41] catalyst. The H—Y[MCM-41] mesostructured zeolitealso maintained its physicochemical integrity even after being boiledfor several days, exhibiting a high 1,3,5-triisopropylbenzene activity(87% conversion after 400 min) even after such severe treatment. SeeFIG. 17. This outcome illustrated the superior hydrothermal stability ofH—Y[MCM-41] over the amorphous Al-MCM-41 catalyst, which lost itsactivity and ordered mesostructure after exposure to similar conditions.

H-ZSM-5 is used as an important additive in cracking catalysts toincrease propylene production and improve octane number in gasoline.Degnan, T. F., et al., Microporous Mesoporous Mater., 2000, 35-36,245-252. However, due to its small pores, it is inactive in1,3,5-triisopropylbenzene cracking at 200° C. (<1% conversion after 400min). The incorporation of MCM-41 mesostructure in this zeolite(H-ZSM-5[MCM-41]) successfully achieved substantial activity, with 40%conversion after 400 min (see FIG. 19). In this case, the activity wasattributed to the mesopores and strong acidity of the mesostructuredzeolite.

More than 135 different zeolitic structures have been reported to date,but only about a dozen of them have commercial applications, mostly thezeolites with 3-D pore structures. Corma, A., Chem. Rev., 1997, 97,2373-2419; Davis, M. E., Nature, 2002, 417, 813-821. The incorporationof 3-D mesopores would be especially beneficial for zeolites with 1-Dand 2-D pore structures as it would greatly facilitate intracrystallinediffusion. To illustrate the potential of mesostructure processing ofzeolites with low pore interconnectivity, H-MOR with 1-D pores wereprepared with MCM-48 mesostructure. The resulting H-MOR[MCM-48] with 3-Dmesostructured structures was examined for the catalytic cracking of1,3,5-triisopropylbenzene at 200° C. It exhibited 50% conversion after400 min, which was significantly higher compared to the 7% conversionachieved by H-MOR (see FIG. 18).

Mesostructured zeolites not only showed much higher catalytic activity,but also enhanced selectivity. For example, H—Y[MCM-41] mesostructuredzeolite produced only 75% of the benzene generated by the H—Y zeolite.See FIG. 16. Benzene is a toxic compound whose presence in gasoline isbeing increasingly restricted by legislation. Degnan, T. F., et al.,Microporous Mesoporous Mater., 2000, 35-36, 245-252. The benzeneproduction was even lower in the case of H-MOR[MCM-48], and was minimalin the case of H-ZSM-5[MCM-41]. The decrease in benzene production hasbeen observed in small zeolite crystals, and was related to theintrinsic ability of crystals with higher surface areas to limitsuccessive cracking reactions. Al-Khattaf, S., et al., Appl. Catal. A:Gen. 2002, 226, 139-153. It also reduced the formation of coke, whichwas the undesired end-product of the cracking process that wasresponsible for catalyst deactivation. Thus, the mesostructured zeolitesnot only provided for higher catalytic activity and selectivity, butalso longer catalyst life time.

Zeolitic nanorods (ZNRs), another form of mesostructured zeolite, alsoenhance catalytic activity by increasing active-site accessibility. Therod-shape ZNRs are only nanometer-sized in diameter, so internaldiffusional resistance is minimal. These new mesostructured zeoliteswere tested as cracking catalysts for the gas oil fraction of petroleumto assess their potential. In the cracking of 1,3,5-triisopropylbenzene,the conventional H-MOR zeolite showed a low activity (7% conversionafter 400 min) due to its medium-sized (0.65×0.70 nm), 1-D pores. Incontrast, H-MOR[ZNR] achieved a much higher catalytic activity undersimilar conditions (˜52% conversion) (see FIG. 20). This significantincrease in catalytic activity was attributed to ZNRs' higher surfaceareas, readily accessible active sites, and improved intracrystallinediffusivity.

Besides increased activity, ZNRs also showed improved selectivity due totheir nanostructured rod-shape morphology. For example, H-MOR[ZNR]produced 3 times less benzene per mole of 1,3,5-triisopropylbenzeneconverted as compared to commercial H-MOR (see FIG. 20). Thissignificant increase in selectivity also helped to reduce cokeformation, which has been a major problem with conventional crackingcatalysts, especially those containing 1-D pores, such as mordenite.

The simple, inexpensive and generalized synthesis strategy describedhere allows for the preparation of ZNR, a crystalline material withwalls that are only several nanometers thick (3-20 nm), in whichnanorings and junctions are common. The novel synthesis strategy wasbased on the “programmed” zeolitic transformation of mesoporousmaterials, which avoided the typical drawbacks of nanoscaled zeolitesynthesis (e.g., low yield, difficulty in separation, and high pressuredrops), and did not require the use of a layered precursor. The uniquecrystalline structure of ZNRs provided for improved catalytic conversionof bulky molecules by increasing the accessibility to its microporosity,while reducing interparticle and intraparticle diffusion barriers.

Mesostructured zeolites were tested for crude oil refining viaMicroactivity Test (ASTM D-3907). This is a well known and widelyaccepted technique to estimate the performance of FCC (Fluid CatalyticCracking) catalysts. Vacuum gas-oil was used as feed in a fluid-bedstainless steel reactor. The experiments were conducted under identicalconditions with mesostructured zeolites and their conventional zeolitescounterparts. The samples were displayed in a fluidized-bed stainlesssteel reactor. Reaction temperature was 500° C., the amount of catalystwas 3.0 g, the catalyst/oil ratio was 2.0, the WHSV was 30 g/h/g, andthe contact time was 60 seconds. These tests showed that usingHY[MCM-41] in place of conventional HY resulted in a 43% increase ingasoline production, a 75% increase in propylene and a 110% increase inbutenes. Additionally, there is a 32% decrease in coke formation, a 23%decrease in Total Dry Gas, and a 12% decrease in LPG (LiquifiedPetroleum Gases). The presence of mesopores in the HY[MCM-41], which hasdouble the surface area of HY, favours the cracking of the largermolecules present in the crude oil, which cannot be transformed withinthe micropores of conventional zeolites. The increase of light olefinswas related to the reduction of hydrogen transfer reaction due to thepresence of thin walls in mesostructured zeolites (˜2 nm) as opposed tothe thick crystals of conventional zeolites (˜1000 nm). This wallthickness also results in reduction of overcracking, significantlyreduces coke formation, and reduces production of Total Dry Gas and LPG.

Pyrolysis of plastics has gained renewed attention due to thepossibility of converting these abundant waste products into valuablechemicals while also producing energy. Williams, P. T. Waste Treatmentand Disposal; John Wiley and Sons, Chichester, UK, 1998, Acidiccatalysts, such as zeolites, have been shown to be able to reducesignificantly the decomposition temperature of plastics and to controlthe range of products generated. Williams, P. T. Waste Treatment andDisposal. John Wiley and Sons, Chichester, UK, 1998; Park, D. W., etal., Polym. Degrad. Stability 1999, 65, 193-198; Bagri, R., et al., J.Anal. Pyrolysis, 2002, 63, 29-41. However, the accessibility of thebulky molecules produced during plastic degradation has been severelylimited by the micropores of zeolites.

The catalytic degradation of polyethylene (PE) by commercially availablezeolites and their corresponding mesostructured zeolites was studied bythermal gravimetric analysis (TGA). In all cases, mesostructuredzeolites allowed for reduced decomposition temperatures compared to thecommercial zeolites (by ˜35° C. in the case of H-ZSM-5[MCM-41] vs.H-ZSM-5), even at high catalyst/PE ratios (see FIG. 21). In fact, at aPE/H-ZSM-5[MCM-41 ] weight ratio of 1:1, a lower decompositiontemperature was achieved compared to that required by a PE/ZSM-5 weightratio of 1:2.

The large accessible surface area and ion-exchange properties ofmesostructured zeolites will also facilitate the surfacefunctionalization, the immobilization of homogeneous catalysts, and thedeposition of metal clusters. Thus, mesostructured zeolites also serveas a very useful catalyst support for a variety of reactions.

With their improved accessibility and diffusivity compared toconventional zeolites, mesostructured zeolites may also be employed inplace of zeolites in other applications, such as gas and liquid-phaseadsorption, separation, catalysis, catalytic cracking, catalytichydrocracking, catalytic isomerization, catalytic hydrogenation,catalytic hydroformilation, catalytic alkylation, catalytic acylation,ion-exchange, water treatment, pollution remediation, etc. Many of theseapplications suffer currently from limitations associated with the smallpores of zeolites, especially when bulky molecules are involved. vanBekkum, H., Flanigen, E. M., Jacobs, P. A., Jansen, J. C. (editors),Introduction to Zeolite Science and Practice, 2nd edition. Studies inSurface Science and Catalysis, Vol. 137, 2001; Corma, A., Chem. Rev.,1997, 97, 2373-2419; Davis, M. E., Nature, 2002, 417, 813-821.Mesostructured zeolites present attractive benefits over zeolites insuch applications.

Organic dye and pollutant removal from water is of major environmentalimportance, and represents the third major use of zeolites (accountingfor 80 tons of zeolites per year). Galo, J. de A. A., et al., Chem. Rev.2002, 102, 4093-4138. However, most of the organic dyes are bulky, whichmake their removal slow or incomplete, requiring a huge excess ofzeolites in the process. Mesostructured zeolites offer significantadvantage over zeolites in organic dye and pollutant removal with theirlarger surface area and pore size.

Kits

This invention also provides kits for conveniently and effectivelyimplementing the methods of this invention. Such kits comprise any ofthe zeolitic structures of the present invention or a combinationthereof, and a means for facilitating their use consistent with methodsof this invention. Such kits provide a convenient and effective meansfor assuring that the methods are practiced in an effective manner. Thecompliance means of such kits includes any means which facilitatespracticing a method of this invention. Such compliance means includeinstructions, packaging, and dispensing means, and combinations thereof.Kit components may be packaged for either manual or partially or whollyautomated practice of the foregoing methods. In other embodimentsinvolving kits, this invention contemplates a kit including blockcopolymers of the present invention, and optionally instructions fortheir use.

EXEMPLIFICATION

The invention now being generally described, it will be more readilyunderstood by reference to the following examples, which are includedmerely for purposes of illustration of certain aspects and embodimentsof the present invention, and are not intended to limit the invention.

Example 1 Synthesis of H—Y[MCM-41]

0.79 g of H—Y (Zeolyst CBV-720 Si/Al=15) were stirred in 50 mL of a 0.37M NH₄OH solution containing 0.55 g of CTAB, for 20 minutes, after whichtime the synthesis mixture was hydrothermally treated at 150° C. for 10hours. The solid was filtered, washed, and finally ramped in nitrogen at5° C./min until 550° C., and then switched to air for 4 hours. Similarconditions were used to calcine all of the samples. Alternatively, 1 gof H—Y (Zeolyst CBV-720 Si/Al=15) was stirred for in 30 mL of a 0.09 Mtetramethylammonium hydroxide (TMA-OH) solution. Then 0.5 g ofcetyltrimethylammonium bromide (CTAB) was added. After 30 minutes ofstirring the suspension was hydrothermally treated for 20 hours at 150°C. Structural parameters are presented in Table 1.

Example 2 Synthesis of H-MOR[MCM-41]

2.0 g of H-MOR (calcined Zeolyst CBV21A Si/Al=10) was stirred in 50 mLof 0.27 M TMA-OH solution. Afterwards, 1.0 g of CTAB was added. Afterother 30 minutes of stirring the synthesis solution was hydrothermallytreated at 150° C. for 20 hours. Structural parameters are presented inTable 1.

Example 3 Synthesis of H-ZSM-5[MCM-41]

1.0 g of NH₄-ZSM-5 (Zeolyst CBV3024E Si/Al=15) was stirred in 50 mL of0.8 M HF solution for 4 hours. This suspension was added to a solutioncontaining 0.69 g of CTAB, and stirred for 30 minutes. The resultingsynthesis mixture was basified by slowly adding 2.5 g of a 30% NH₄OHsolution. Finally, it was hydrothermally treated at 150° C. for 20hours. Structural parameters are presented in Table 1. The wallthickness was determined by the standard method within the art bysubtracting the distance between two pore centers (a_(o), obtained viaX-ray diffraction) and the pore size (determined by N₂ adsorption).

TABLE 1 Structural parameters for the mesostructured zeolites. a_(o)(nm) Pore diameter (nm) Wall thickness (nm) H-Y[MCM-41] 4.2 2.6 1.6H-MOR[MCM-41] 4.7 2.5 2.2 H-ZSM-5[MCM-41] 4.8 2.6 2.2

Example 4 Catalytic Cracking of Cumene and 1,3,5-triisopropylbenzene

Catalytic tests were carried out in a lab-scale packed-bed catalyticreactor connected to a gas chromatograph (Hewlett Packard HP6890 Series)with a DB petrol (50 m×0.2 mm×0.5 microns) column. In all cases, 50mL/min of He were flowed through 50 mg of catalyst. For cumene crackingthe gas flow was saturated with cumene at room temperature and thereaction temperature was 300° C. For 1,3,5-triisopropylbenzene crackingthe gas flow was saturated at 120° C. and the reaction temperatures were300° C.

Example 5 Polyethylene (PE) Degradation

An initial mass of ˜10 mg of catalyst:PE samples with ratios 1:2, 1:1,and 2:1 were ramped in a thermogravimetric analyzer (Perkin Elmer TGA7)at 10° C./min in a 250 mL/min flow of He until 600° C. Results aredepicted in FIG. 21.

Example 6 Chemical Species and Homogeneous Anchoring on MesostructuredZeolites

The acid form of the mesostructured zeolite with faujasite structure andMCM-41 architecture, H—Y[MCM-41], (Si/Al˜15), was ion exchanged in a 0.1M NH₄OH solution for 24 h in order to produce NH₄—Y[MCM-41]. Theresulting material was ion-exchanged again in a 7.0 mM NH₂(CH₂)₂NMe₃Clsolution for 24 h. After filtering and washing thoroughly, the samplewas dried at 60° C. overnight. Finally, this amine functionalizedmesostructured zeolite was added to a 2.0 mM Rh(PPh₃)₃ solution(Wilkinson catalyst) for 24 h. After filtering and washing thoroughly,the sample was dried at 60° C. overnight. All the products, as well asthe quaternary amine and the Wilkinson catalyst, were analyzed by FTIRto confirm the presence of the different species on the mesostructuredzeolite even after thorough washing (see FIG. 22).

INCORPORATION BY REFERENCE

All of the patents and publications cited herein are hereby incorporatedby reference.

EQUIVALENTS

Those skilled in the art will recognize, or be able to ascertain usingno more than routine experimentation, many equivalents to the specificembodiments of the invention described herein. Such equivalents areintended to be encompassed by the following claims.

1-42. (canceled)
 43. A method of catalytically cracking an organiccompound comprising contacting the organic compound with amesostructured zeolitic one-phase hybrid material having long-rangecrystallinity and comprising a plurality of mesopores.
 44. The method ofclaim 43 wherein the organic compound comprises at least one of ahydrocarbon, unsaturated hydrocarbon, aromatic hydrocarbon, alkylatedbenzene, 1,3,5-triisopropyl benzene, crude oil, gas-oil, or vacuum gasoil.
 45. The method of claim 43 wherein the mesostructured zeoliticone-phase hybrid material has a zeolitic structure of a faujasite (FAU),mordenite (MOR), or ZSM-5 (MFI).
 46. The method of claim 43 wherein themesostructured zeolitic one-phase hybrid material has the hexagonal porearrangement of MCM-41.
 47. The method of claim 43 wherein themesostructured zeolitic one-phase hybrid material is Y[MCM-41],MOR[MCM-41], or ZSM-5[MCM-41].
 48. The method of claim 43 wherein themesostructured zeolitic one-phase hybrid material exhibits a sharpnitrogen uptake at a partial pressure [P/P_(o)] higher than a partialpressure indicating microporosity.
 49. The method of claim 48 whereinthe higher partial pressure of the sharp nitrogen uptake of themesostructured zeolitic one-phase hybrid material is between about 0.2and 0.6.
 50. The method of claim 49 wherein the higher partial pressureof the sharp nitrogen uptake of the mesostructured zeolitic one-phasehybrid material is about 0.3.
 51. The method of claim 43 wherein themesostructured zeolitic one-phase hybrid material has a faujasite (FAU),mordenite (MOR), or ZSM-5 (MFI) structure.
 52. The method of claim 43wherein the plurality of mesopores of the mesostructured zeoliticone-phase hybrid material comprise a mean pore diameter from about 2 toabout 5 nm.
 53. The method of claim 43 wherein the plurality ofmesopores of the mesostructured zeolitic one-phase hybrid material havea wall thickness from about 1 to about 5 nm.
 54. The method of claim 43wherein the plurality of mesopores of the mesostructured zeoliticone-phase hybrid material have a pore size distribution that is narrow.55. The method of claim 43 wherein the plurality of mesopores of themesostructured zeolitic one-phase hybrid material comprise a pore sizediameter distribution having a range of from about one half to aboutdouble the average pore size diameter.
 56. The method of claim 43wherein the plurality of mesopores of the mesostructured zeoliticone-phase hybrid material define a mesopore pore volume, a majority ofthe mesopore pore volume having a pore size diameter distribution rangeof from about one half to about double the average pore size diameter.57. The method of claim 43 wherein the mesostructured zeolitic one-phasehybrid material is a faujasite.
 58. The method of claim 43 wherein themesostructured zeolitic one-phase hybrid material has a mesoporousvolume adsorption of at least about 0.05 cc/g.
 59. The method of claim43 wherein the mesostructured zeolitic one-phase hybrid material has amesoporous volume adsorption of at least about 0.1 cc/g.
 60. The methodof claim 43 wherein the mesostructured zeolitic one-phase hybridmaterial has a mesoporous volume adsorption of at least about 0.2 cc/g.61. The method of claim 43 wherein the mesoporosity of themesostructured zeolitic one-phase hybrid material is arranged.
 62. Themethod of claim 61 wherein the arrangement produces one or moredistinctive XRD peaks at two theta values between 0 and 8 two thetaangle degrees.
 63. A method of catalytically cracking an organiccompound comprising contacting the organic compound with a hybridone-phase mesostructured zeolitic material having long-rangecrystallinity and comprising a plurality of mesopores, such that thelong-range crystallinity results in XRD peaks at two theta angle degreeshigher than
 8. 64. The method of claim 63 wherein the organic compoundcomprises at least one of a hydrocarbon, unsaturated hydrocarbon,aromatic hydrocarbon, alkylated benzene, 1,3,5-triisopropyl benzene,crude oil, gas-oil, or vacuum gas oil.
 65. The method of claim 63wherein the hybrid one-phase mesostructured zeolitic material has azeolitic structure of a faujasite (FAU), mordenite (MOR), or ZSM-5(MFI).
 66. The method of claim 63 wherein the hybrid one-phasemesostructured zeolitic material has the hexagonal pore arrangement ofMCM-41.
 67. The method of claim 63 wherein the hybrid one-phasemesostructured zeolitic material is Y[MCM-41], MOR[MCM-41], orZSM-5[MCM-41].
 68. The method of claim 63 wherein the hybrid one-phasemesostructured zeolitic material has a mesoporous volume adsorption ofat least about 0.1 cc/g.
 69. The method of claim 63 wherein the hybridone-phase mesostructured zeolitic material is a faujasite.
 70. Themethod of claim 63 wherein the hybrid one-phase mesostructured zeoliticmaterial has a mesoporous volume adsorption of at least about 0.05 cc/g.